DE2038749B2 - PROCESS FOR THE PRODUCTION OF (METH) ACROLEIN BY OXYDATION OF PROPYLENE OR ISOBUTENE - Google Patents

Description

corresponds, in which L is phosphorus and / or arsenic and / or boron, M is potassium and / or rubidium and / or cesium, α and b each have a value from 0 to 15, where α and b taken together have a value from 2 to 15, c has a value from 0.5 to 7, d has a value from 0.1 to 4, e has a value from 0 to 4, / has the value 12, g has a value from 35 to 85 and h has a value of 0.01 to 0.5. ν

corresponds, in which L is phosphorus and / or arsenic and / or boron, M is potassium and / or rubidium and / or cesium, α and b each have a value from 0 to 15, where α and b taken together have a value

ίο from 2 to 15, c has a value from 0.5 to 7, d has a value from 0.1 to 4, e has a value from 0 to 4, / has the value 12 , g has a value from 35 to 85 and h has a value of 0.01 to 0.5.

The catalysts of the invention differ from the aforementioned known catalysts in that they contain potassium and / or rubidium and / or cesium.

The preferred catalysts have the following composition:

20th

A) b = 0, a = 3 to 11, c = 1 to 3, d = 1 to 3, e = 0.5 to 1, / = 12, h = 0.1 to 0.3 and g = 45 to 70.

B) a = 0, b = 2 to 7, c = 1 to 3, d = 1 to 3, e = 0.5 to 1, f = 12, h = 0.1 to 0.3 and g = 45 to 70.

C) Neither α nor b = 0, α <11, b < 7, a + b = 2 to 11, c = 1 to 3, d = 1 to 3, e = about 1, / = 12, g = 45 to 70 and h = 0.1 to 0.3.

30 ⁽ Since the catalysts do not have significantly improved properties when two or more of the elements potassium, rubidium and cesium are present at the same time and rubidium and cesium are expensive, the catalysts according to the invention preferably contain only potassium as metal M. The catalysts used in the process of the invention are produced by

In the USA. Patent 3,454,630 and Canadian Patent 781,513 Φ see processes for the preparation of unsaturated aldehydes by oxidation; of: propylene described in the vapor phase.

According to the process described in US Pat. No. 3,454,630, propylene is oxidized to acrolein over a catalyst consisting of nickel, cobalt, iron, bismuth, phosphorus and molybdenum oxide. In a single pass, a maximum acrolein yield of 71 ^e / ₀ of theory is achieved. Following the procedure described in Canadian Patent 781 513 method in which ^häupt-: a plural is used from nickel, cobalt, iron, bismuth, arsenic and molybdenum oxide catalyst existing in a single pass, a maximum acrolein yield is of 75.5% achievable.

The object of the invention was to improve the aldehyde yield of the known processes with the aid of a new catalyst to increase.

The invention thus relates to a process for the preparation of (meth) acrolein by oxidizing propylene or isobutene with oxygen or free oxygen-containing gases in the vapor phase at temperatures of 250 to 500 ° C. and pressures of 0.5 to 10 kg / cm ² in the presence of nickel, cobalt, iron, bismuth, molybdenum and optionally phosphorus-containing oxide catalysts, which is characterized in that the oxidation is carried out in the presence of an oxide catalyst whose addition

a) an aqueous molybdate solution, optionally phosphoric acid and / or arsenic acid and / or Boric acid was added, with at least one potassium and / or rubidium and / or cesium salt, at least one water-soluble iron compound and at least one water-soluble Bismuth compound and optionally at least one water-soluble cobalt compound and optionally at least one water-soluble nickel compound is added and

b) the resulting suspension slurry, optionally after the addition of a carrier, is dried and added high temperatures in the presence of oxygen or gases containing free oxygen calcined.

As molybdates in the method of the invention, for. B. ammonium molybdate, molybdenum oxide or molybdic acid be used.

Potassium, iron, bismuth, nickel and cobalt compounds are, for example, the corresponding Nitrates used. Potassium is used in the form of potassium molybdate.

The method of the invention is particularly useful for the selective oxidation of propylene to acrolein. The oxidation of propylene to z. B. acrylic acid, Carbon monoxide or carbon dioxide is suppressed in the process. The maximum acrolein yield per pass is 88% of theory.

3 4

It means here:

^Mo1 converted propylene

Degree of conversion of propylene (P),% = selectivity of acrolein formation (A),% =

Moles of propylene used

Moles of converted propylene

,. . , _, m Ai in moles of acrolein formed

Acrolein yield per pass (P χ A),% = ² '1 °°

Moles of propylene used

. . ~ n, moles of acrylic acid formed, ...

Acrylic acid yield per pass,% = ¹⁰ °

Moles of propylene used

The catalyst is used in the process of the invention

preferably in combination with a carrier incorporated ao catalyst 2

puts. Examples of suitable supports are silica, silicon carbide and alumina. One works particularly well as in the production of catalysis are silica gel or sol. Sator 1, however, instead of phosphoric acid

The catalyst is used in the form of granules or 10.3 g of arsenic acid. One receives a Kataly tablets used. In general, it is used as a fixed bed of the composition, but fluid beds or beds are also used.
Fluidized beds applicable. Ni ₁ Co ₃ Fe ₈ Bi ₁ As ₁₁₆ K ₀₁₈ Mo ₁₂ O ₄₈₁₃₅ .

The oxidation process according to the invention is
preferably at temperatures of 300 to 45O ⁰ C

and preferably in the presence of steam 3 ° catalyst 3

carried out. In the case of the oxidation of propylene

is the contact time of a gaseous mixture.

from propylene, air and water vapor with normalizer 1, but instead of phosphoric acid press for 0.5 to 8 seconds. The gas mixture that used over 4.4 g of boric acid. A catalyst is obtained Catalyst is to be passed, is mixed by the composition of the olefin with air and water vapor in by the converter

an oxygen / water / olefin molar ratio of Ni ₁ Co ₃ Fe ₂ BIiP ₂ Ko 2Mo ₁₂ O ₄₉ ,,.

(0.5 to 4): (1 to 20): 1 made. In the case of oxidation of propylene, a preferred starting gas molar ratio is 8 to 15 moles of air / 1 to 6 moles of 40, Water vapor / mole propylene. Catalyst 4 The examples illustrate the invention.

You work like in the production of catalytic

However, Catalyst 1 ^{sator!> At Ste} U ^e of the potassium nitrate is 1.9 g

45 rubidium nitrate is used, and in place of the phos-

8.7 g of nickel nitrate in 5 ml of distilled phosphoric acid are used with 7.0 g of arsenic acid. Man er water 26.2 g of cobalt nitrate in 10 ml of distilled holds a catalyst's composition Water, 24.2 g iron (III) nitrate in 8 ml distilled

Water and 14.5 g of bismuth nitrate in 10 ml of distilled Ni ₁ Co ₃ Fe ₂ Bi ₁ P ₁ Rb ₀ ^ MOi ₂ O _{49 7S} .

Water that is mixed with 3 ml of concentrated nitric acid
was acidified, dissolved. These four nitrate solutions are mixed together. _v . '■

A solution of 7.0 g of 85% strength Phos catalyst 5 is also used

phosphoric acid and 0.67 g of potassium nitrate in 5 ml of distilled

Water in a solution of 63.6 g of aramonium molybdenum. The procedure is as for the production of catalydate registered in 64 ml of distilled water. Here sator 1, but instead of rubidium nitrate a light yellow aqueous solution is obtained. This used 2.6 g of cesium nitrate. You get one Solution is mixed with the aforementioned nitrate catalyst of the composition solution added.

The pulpy suspension obtained is mixed with 17 g of 60 Ni ₁ Co ₃ Fe ₂ Bi ₁ P ₂ Cs ₀ ^ Mo ₁₂ O ₄₉₁₉ .

Silica sol added, dried by heating,
further heated, then cooled and finally

pulverized. The powder obtained becomes tablets of catalysts 6 to 12

processed, and the pellets are 6 hours at the

Air calcined at 500 ⁰ C. A catalyst is obtained. The procedure is similar to that for the production of catalyst with the composition catalyst 1. Table I shows the proportions of the starting materials used and the combined NiICo ₃ Fe ₂ Bi ₁ P ₂ Kc ₂ Mo ₁₂ O ₄ J _e . Settlement of the catalysts can be seen.

Table I.

Kata-
lysator Nickel nitrate Cobalt nitrate EisenCIII) -
nitrate bismuth
nitrate phosphorus
acid Potassium nitrate Ammonium-
molybdate Saltpetre
acid pebble
acid sol (S) (G) (S) (6) (G) (e) (G) (ml) (G) 6th 8.7 26.2 24.2 14.5 3.5 0.33 63.6 3 17th 7th 8.7 26.2 24.2 14.5 10.5 0.99 63.6 3 17th 8th 61.2 12.1 7.3 3.5 0.33 63.6 1.5 16.7 9 95.7 12.1 7.3 3.5 0.33 63.6 1.5 18.6 10 26.1 43.7 36.3 14.5 3.5 0.33 63.6 3.0 19.0 11th 26.1 43.7 36.3 43.5 3.5 0.33 63.6 3.0 21.9 12th 34.8 52.4 72.7 14.5 3.5 0.33 63.6 3.0 34.6

catalyst

Catalyst composition

6 Ni ₁ Co ₃ Fe ₂ Bi ₁ P ₁ K ₀₄ Mo ₁₂ O _{47 01}

7 Ni ₁ Co ₃ Fe ₂ Bi ₁ P ₃ K ₀₁₃ Mo ₁₂ O ₅₂₄₅

8 Co ₇ Fe ₁ Bi ₀₁₅ P ₁ K ₀₄ Mo ₁₂ O _{47 180}

9 Ni ₁₁ Fe ₁ Bi _0-5 P ₁ K ₀₄ Mo ₁₂ O ₅₁₁₈₀

10 Ni ₃ Co ₅ Fe ₃ Bi ₁ P ₁ K ₀₄ Mo ₁₂ O _62-55

11 Ni ₈ Co ₀ Fe ₃ Bi ₃ P ₁ K ₀₄ Mo ₁₂ O ₅₅₁₅₅

12 Ni ₄ Co ₄ Fe ₄ Bi ₁ P ₁ K ₀₄ Mo ₁₂ O ₅₈₁₀₅

example 1

cm ^{3 of} the catalyst 1 are placed in a reactor which has an internal diameter of 20 mm and which is immersed in a molten salt composed of potassium nitrate. Propylene is then oxidized in this reactor under the following conditions:

Temperature of the potassium nitrate bath, ⁰ C 305 molar ratio propylene / air / water

steam 1: 10: 5

Dwell time, 1.5 seconds

20th

The following results are achieved:

Degree of conversion of propylene,

° / o of theory 96

Selectivity of acrolein formation,% .. 92

* ⁵ acrolein yield per pass,% 88

Acrylic acid yield per pass,% 3

This oxidation also produces small amounts of carbon monoxide, carbon dioxide and acetic acid as by-products.

B e i s ρ i e 1 e 2 to 12

The procedure of Example 1 is repeated except that the conditions shown in Table II are used applied. Table II also shows the results.

Table II

at
game Kata
lyser Catalyst composition bath
tempe
rature Stay
Time Conversion
lung
degree of
Propylene Selek
activity
the
Acrolein
education Acrolein
yield
Per
By
corridor acrylic
acid-
yield
Per
By
corridor ( ⁰ C) (Sec.) (V,) (%) (° /.) OV,) 2 2 NiICo ₃ Fe ₂ Bi ₁ As ₁₁₆ K ₀₁₂ Mo ₁₂ O ₄₈₁₃₆ 305 1.5 94 93 87 4th 3 3 Ni ₁ Co ₃ Fe ₂ Bi ₁ B ₂ K ₀₁₂ Mo ₁ JsO ₄₉₁₆ 310 1.5 95 86 82 6th 4th 4th Ni ₁ Co ₃ Fe ₂ Bi ₁ P ₁ Rb ₀₁₄ Mo ₁₂ O _49-75 310 1.5 95 89 84 5 5 5 Ni ₁ COsFe ₂ Bi ₁ P ₂ Cs ₀₁₄ Mo ₁₂ O ₄₉ ,, 320 1.5 93 86 80 7th 6th 6th Ni ₁ Co ₃ Fe ₂ Bi ₁ P ₁ K ₀₄ Mo ₁₂ O ₄₇₁ O ₁ 305 1.5 95 90 85 4th 7th 7th Ni ₁ Co ₃ Fe ₂ Bi ₁ P ₃ K ₀₃ Mo ₁₂ Os ₂₄₅ 315 1.5 95 85 81 5 8th 8th Co ₇ Fe ₁ Bi ₀₁₅ P ₁ K ₀₄ Mo ₁₂ O ₄₇ g 320 1.5 95 86 82 5 9 9 Ni ₁₁ Fe ₁ Bi ₀₁₆ P ₁ K ₀₄ Mo ₁₂ O ₅₁₁₈₀ 310 1.5 96 87 83 6th 10 10 Ni ₃ Co ₅ Fe ₃ Bi ₁ P ₁ K ₀₄ Mo ₁₂ O ^ s ₅ 305 1.6 95 91 86 4th 11th 11th Ni ₃ Co ₅ Fe ₃ Bi ₃ P ₁ K ₀₄ Mo ₁₂ O ₅₅₁₅₅ 325 1.5 95 89 84 5 12th 12th Ni ₄ Co ₆ Fe ₀ Bi ₁ P ₁ K ₀₄ Mo ₁₂ O ₅₉₁₀₅ 315 1.5 96 83 80 10

B e i s ρ i e 1 e 13 to 23

concentrated nitric acid was added to the solution B and 1.7 g orthophosphoric acid and 0.22 g 22.0 g nickel nitrate, 39.4 g cobalt nitrate and 36.6 g 65 potassium nitrate in distilled water to form solution C iron (III) nitrate are dissolved in as little water as possible. This will bring up solutions A, B and C under to solution A dissolved. 14.6 g of bismuth (HI) nitrate are stirred with an aqueous solution of 63.5 g of ammoin 25 ml of distilled water previously combined with 3.6 ml of sodium molybdate. The received brcifönm'ge

Suspension is mixed with 90.5 g silica sol, dried, and heated to 300 ⁰ C. After cooling, the mass is pulverized, processed into cookies and ^{calcined at 700 °} C. for more than 4 hours. The catalyst obtained has the composition:

110 ml of the catalyst prepared in this way are placed in a reactor with an internal diameter of 21.6 mm. The reactor is immersed in a molten salt of potassium nitrate (280 to 380 ^° C.) and, with a residence time of 2 to 5 seconds, from an isobutene-oxygen steam table

flows through, the molar ratios 1: 1.2 to 4.0: 3.0 to 12.0.

The results obtained are shown in Table ΠΙ at various pressures. The reaction products are identified by gas chromatography and acid base titration. Methacrolein, Acetone, acetic acid, carbon dioxide and carbon monoxide are determined as the main products.

For comparison, a catalyst is used while maintaining the reaction conditions mentioned in Example 13 used, which was prepared in the manner described above, but does not contain potassium.

The results of the comparative experiment are also shown in Table III.

Table III

example catalyst
composition Molar ratio bath
tempe
rature Gas pressure Conversion
degree of efficiency
of the iso
butens MeUV
acrolein
yield
Per
By
corridor Selectivi
activity of
Meth
acrolein
education (C4H,: O,: H, O) ( ⁰ C) (atm. abs.) (%) ( ¹ Vo) 13th 1: 2.2: 5.0 345 Normal pressure 98.2 70.1 71.0 14th 1: 2.2: 5.0 280 Normal pressure 90.5 65.3 72.1 15th 1: 2.2: 5.0 360 Normal pressure 97.2 63.2 65.1 16 1: 2.2: 5.0 380 Normal pressure 98.9 60.7 61.4 17th 1: 2.2: 5.0 350 2.0 94.5 64.9 68.7 18th Ni ₈₁₆ Co ₄ ^ Fe ₈₁₀ 1: 2.2: 5.0 350 3.0 93.2 60.7 65.2 19th 1: 2.2; 5.0 354 3.5 95.6 57.6 60.3 20th 1: 1.2: 6.2 345 Normal pressure 85.2 61.6 72.4 21 1: 4.0: 6.2 350 Normal pressure 97.7 63.6 62.1 22nd 1: 2.2: 12.0 355 Normal pressure 94.5 69.8 73.9 23 1: 3.0: 20 345 Normal pressure 95.5 62.4 65.3 Comparison Ni _ii5 Co _4i5 Fe _8i0 1: 2.2: 5.0 330 Normal pressure 95.2 38.6 40.5 example Bij> _0iB Mo _ia O _S 4

B e i s ρ i e 1 e 24 to 31

The procedure described in Examples 13-23 is repeated except that those shown in Table IV become apparent Changes made to the catalyst composition. In particular, the phosphorus content (e) and the proportion of potassium or cesium (h) varies.

If, in Example 1, K ₀ ,, is replaced by Rb _Oi4 or P _{0> 2} by B _g0 , similar yields of methacrolein are obtained.

Table IV

phosphorus number of Cesium Bath temperature Conversion Methacrolein Selectivity of example atoms potassium atoms degree of yield per Methacrolein (e) atoms (H) ( ⁰ Q Isobutene Passage education 1.0 (H) _ 342 ("/.) C /.) (° /.) 24 2.0 0.1 - 350 95.2 69.7 73.0 25th 2.0 0.2 - 350 97.4 68.5 70.5 26th 0.5 0.3 - 340 96.5 65.2 67.8 27 0.5 0.05 - 345 97.2 69.3 71.3 28 0.5 0.5 0.3 345 96.5 65.5 67.8 29 0.5 - 0.5 350 97.0 67.9 69.9 30th - - - 345 96.0 64.3 67.3 31 0.02 96.5 62.1 64.3

Example 32

100 ml of the catalyst 8 are placed in a reactor and at 355 ° C. with a residence time of 3.2 seconds of an isobutene-air-steam mixture of the same molar composition as in Example 13 flows through.

309 516/533

9 10

The following results are achieved:

Degree of conversion of isobutene 96%

Methacrolein yield per pass <68.5%

Selectivity of methacrolein formation 71.4%

Examples 33 to 36

The process and the preparation of the catalyst are carried out as in Example 13, however the catalyst composition is changed as shown in Table V using arsenic. The results are shown in Table V.

Table V

Ni Co Catalyst composition Bi As K Mon Conversion Methacrolein selectivity at 4.5 4th 1 1.0 0.07 12th degree of efficiency yield per the meth game 4.5 4th Fe 1 0.5 0.05 12th of isobutene Passage education 3.0 2 1 1 0.5 0.1 12th (%) (7o) (7,) 33 0 7th 1 1 0.5 0.07 12th 94.3 68.5 72.6 34 2 95.5 67.9 71.2 35 3 95.0 68.9 72.5 36 96.1 69.5 72.3

B e i s ρ i e 1 e 37 to 45

The procedure and the preparation of the catalyst are carried out as in Example 13, but the catalyst composition is changed as described in Table VI. The reaction results are shown in Table VI. "^;

Table VI

Ni Co Catalyst composition Bi P. K Mon Conversion Methacrolein selectivity
J \ ^ + * X ^ α 4-t ^ at 0 12th 1 0.5 0.07 12th degree of efficiency yield per the MeIa-
3f * t * o1f * in game 0 8th Fe 1 0.5 0.07 12th of isobutene Passage education 0 8th 3 3 0.0 0.07 12th (7 ") (° / o) (7o) 37 1 8th 3 1 0.2 0.07 12th 93.2 61.9 66.4 38 2.5 4th 3 1 0.5 0.07 12th 95.0 63.8 67.2 39 2.5 4th 5 0.5 0.5 0.07 12th 93.5 63.7 68.2 40 2.5 5 2 2 0.5 0.07 12th 91.5 61.6 67.3 41 10 1 2 1 0.5 0.07 12th 90.4 61.8 68.5 42 1 2 3 1 0.5 0.07 12th 80.9 54.3 67.2 43 3 86.3 60.1 69.8 44 6th 95.0 55.2 58.1 45 87.7 57.8 65.9

B e i s ρ i e 1 e 46 to 49

The procedure is analogous to the preparation of catalyst 1 and the propylene oxidation according to Example 1 is carried out. The results obtained are shown in Table VII.

Table VII

at
game Catalyst composition Badtem
temperature
( ⁰ C) Usable
Time
(Sec.) Conversion
degree of
Propylene
(7.) Selek
activity of
Acrolcin
education
(7.) Acrolein
yield
Per
By
corridor
(7o) acrylic
acidic
prey per
By
corridor 46
47
48
49 Ni ₃ Co ₄ Fe ₃ Bi ₁ P ₀₅ As ₀₁₅ B ₀₁₅ K _0-1 Mo ₁₂ O _52-3
Ni ₃ Co ₄ Fe ₃ BiJP _0-7 As _0-8 K _0-1 Mo ₁₂ O _52-8
Ni ₃ Co ₄ Fe ₃ Bi ₁ As _0-8 B _0-7 K _0-1 Mo ₁₂ O _52-1
Ni ₃ Co ₄ Fe ₃ Bi ₁ P ₀₁₈ B ₀₈ K _0-1 Mo ₁₈ O ₅₂₁₂₅ 305
305
305
305 1.5
1.5
1.5
1.5 95
95
94
93 87
90
85
86 82
85
80
80 6th
4th
4th
5

Claims (1)

Claim: Process for the production of (methacrolein by oxidation of propylene or isobutene with oxygen or gases containing free oxygen in the vapor phase at temperatures from 250 to 500 ⁰ C and pressures from 0.5 to 10 kg / cm ² in the presence of nickel, cobalt, iron , Bismuth, molybdenum and optionally phosphorus-containing oxide catalysts, characterized in that the oxidation is carried out in the presence of an oxide catalyst, the composition of which does not take into account the carrier content of the empirical formula composition without taking into account the carrier content of the empirical formula